EP0592691A1 - Gasket for automotive engine transmission - Google Patents
Gasket for automotive engine transmission Download PDFInfo
- Publication number
- EP0592691A1 EP0592691A1 EP93911954A EP93911954A EP0592691A1 EP 0592691 A1 EP0592691 A1 EP 0592691A1 EP 93911954 A EP93911954 A EP 93911954A EP 93911954 A EP93911954 A EP 93911954A EP 0592691 A1 EP0592691 A1 EP 0592691A1
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- EP
- European Patent Office
- Prior art keywords
- gasket
- parts
- transmissions
- motor vehicle
- vehicle engines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Definitions
- the present invention relates to gaskets for motor vehicle engines and transmissions.
- Gaskets for motor vehicles are used for sealing off the covers to be attached to the cylinder heads of motor vehicle internal combustion engines, and can be checked for suitability including that of the material thereof when subjected to thermal loads and vibrations during operation. More specifically, they must be resistant to cold for starting engines in a cold state and resistant to heat under high-speed loads. If the engine oil or transmission oil leaks owing to a temperature difference between the intake side and the exhaust side of the engine or to the angle at which the engine is mounted on the vehicle, the oil will drip onto the exhaust pipe in view of the construction of the engine, so that the gasketed portion is exposed to a great fire hazard.
- An object of the present invention is to provide a gasket for motor vehicle engines and transmissions which is made of a vulcanized rubber prepared from a homogeneous dispersion of fluorine-containing polymer and acrylic elastomer and not undergoing phase separation, the gasket having outstanding heat resistance, mechanical strength when hot and resistance to engine oil bubbling as characteristics imparted thereto by the respective materials.
- Another object of the invention is to provide a gasket for motor vehicle engines and transmissions which is excellent also in compression set (CS), resistance to ATF (Automatic Transmission Fuel), resistance to LLC (Long Life Coolant) and durability.
- CS compression set
- ATF Automatic Transmission Fuel
- LLC Long Life Coolant
- the present invention provides a gasket for motor vehicle engines and transmissions which is prepared from a crosslinkable composition comprising 100 parts by weight of a polymer, 0.1 to 100 parts by weight of a filler and 0.1 to 10 parts by weight of a crosslinking agent, the polymer being obtained by dissolving or swelling an amorphous fluorine-containing polymer in an acrylic monomer and subsequently polymerizing the monomer into a high polymer.
- the gasket has outstanding properties in respect of heat resistance, mechanical strength in a hot state and resistance to engine oil bubbling which properties are unexpectable from mere blends of fluorine-containing polymers and acrylic elastomers as kneaded together.
- the gasket of the invention for motor vehicle engines and transmissions is excellent also in compression set, ATF resistance, LLC resistance and durability.
- Examples of amorphous fluorine-containing polymers which can be dissolved or swollen in acrylic monomers for use in the present invention are vinylidene fluoride/hexafluoropropylene, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene, vinylidene fluoride/chlorotrifluoroethylene and like vinylidene fluoride copolymers, tetrafluoroethylene/propylene, hexafluoropropylene/ethylene and fluoro(alkyl vinyl ether) (including those having a multiplicity of ether bonds)/olefin copolymers, fluorosilicone rubber, fluorophosphazene rubber, etc.
- vinylidene fluoride/hexafluoropropylene Preferable among these are vinylidene fluoride/hexafluoropropylene, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene and vinylidene fluoride/chlorotrifluoroethylene polymers.
- amorphous refers to elastomers the melting point of which is not observable substantially at the peak of DSC (Differential Scanning Colorimeter).
- Acrylic monomers for use in the present invention are not limited and include mono- and poly- functional monomers. Such monomers are used singly, or at least two of them are used in combination. Preferably, polyfunctional monomers are used in a small amount in combination with a monofunctional monomer.
- MMA methyl methacrylate
- EMA ethyl methacrylate
- BMA butyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- GMA glycidyl methacrylate
- MEMA 2-methoxyethyl methacrylate
- MSPM 2-(phenylphosphoryl)ethyl methacrylate
- HNPM 2-hydroxy-3-( ⁇ -napthoxy)propyl methacrylate
- NPG-GMA ethylene glycol dimethacrylate
- EDMA or 1G diethylene glycol dimethacrylate
- DIEDMA or 2G diethylene glycol dimethacrylate
- TriEDMA or 3G triethylene glycol dimethacrylate
- TEDMA tetraethylene glycol dimethacrylate
- CH2 CFCOOCH2CF2CF2H (4FFA)
- CH2 CFCOOCH2CF2CF3 (5FFA)
- CH2 CFCOOCH2(CF2)3CF2H (8FFA)
- CH2 CFCOOCH2(CF2)5CF2H (12FFA).
- the monomer may have admixed therewith a small amount of acrylonitrile, 2-chloroethyl vinyl ether, vinyl monochloroacetate, methylvinyldichlorosilane or the like.
- the polyfunctional monomer it is suitable to use the polyfunctional monomer in an amount of 1 to 20 parts (by weight, the same as hereinafter) per 100 parts by weight of the monofunctional monomer.
- the proportions of the amorphous fluorine-containing polymer and the acrylic monomer to be used in the present invention can be determined suitably. It is generally desirable to use 5 to 1000 parts of the latter per 100 parts of the former.
- the fluorine-containing polymer is dissolved or swollen in the acrylic monomer, which is then polymerized into a high polymer.
- the polymerization is conducted in the presence of a polymerization initiator.
- a polymerization inhibitor, reducing agent, transfer agent, etc. can be added to the polymerization system.
- useful polymerization initiators are light, heat, benzoyl peroxide, azoisobutyronitrile (AIBN), camphorquinone (CQ), 9-fluorenone, tributylborane (TBB), benzophenone and the like.
- Examples of useful reducing agents are dimethylaminoethyl methacrylate (DMAEMA), dimethyl-p-toluidine (DMPT) and the like.
- Examples of useful polymerization inhibitors are hydroquinone, hydroquinone methyl ester and the like.
- Examples of useful transfer agents include lauryl mercaptan.
- IPN interpenetrating polymer network
- IPN is a polymer obtained by mixing two linear polymers together each in the form of a liquid (or solution) and crosslinking one or both of the polymers to interlock the respective molecular chains.
- the following method is usually employed. A monomer for forming a guest polymer is injected into the high polymer formed. Alternatively, the polymer is immersed in or injected into a solution containing the monomer. The mixture is then polymerized by heating, irradiation with light or like procedure, a filler, crosslinking agent, etc. are admixed with the resulting polymer, and the mixture is crosslinked. Other methods are also usable.
- fillers useful for the present invention are carbon black, silica, clay, kieselguhr, talc, calcium carbonate and like reinforcing agents.
- the filler is used preferably in an amount of 0.1 to 100 parts per 100 parts of the polymer. If the amount is less than 0.1 part, an insufficient reinforcing effect will result, whereas if the amount is over 100 parts, the composition fails to exhibit rubberlike properties.
- crosslinking agents useful for the invention are those for use in crosslinking vinylidene fluoride-containing rubbers, such as peroxides, polyols and polyamines. More specific examples are Perhexa 2.5B (peroxide manufactured by Nippon Oils & Fats Co., Ltd.), triallyl isocyanurate (TAIC) bisphenol AF, N,N'-dicinnamylidene-1,6-hexadiamine, etc.
- the crosslinking agent is used preferably in an amount of 0.1 to 10 parts per 100 parts of the polymer. If the amount is less than 0.1 part, the degree of crosslinking achieved is insufficient, whereas if the amount is in excess of 10 parts, the composition is unlikely to exhibit rubberlike properties.
- nitrogen- or phosphorus- containing organic tertiary or quaternary compounds as crosslinking accelerators, oxides or hydroxides of bivalent metals as an acid-acceptor, and compounds containing a plurality of vinyl or allyl groups and serving as auxiliary crosslinking agents.
- antioxidants processing assisting agents, scorch retarders, antiozonants, ultraviolet absorbers, flame retardants, plasticizers and other additives.
- the gasket for motor vehicle engines and transmissions which is obtained according to the invention by dissolving or swelling the fluorine-containing polymer in the acrylic monomer and subsequently polymerizing the monomer is unexpectedly exceedingly superior in heat resistance, mechanical strength when hot and resistance to engine oil bubbling to those obtained from a mere blend of fluorine-containing polymer and acrylic elastomer.
- the gasket of the invention for motor vehicle engines and transmissions is excellent also in compression set, ATF resistance, LLC resistance and durability.
- the composition of the invention has a slightly higher viscosity than usual simple blended rubber materials, so that when comprising a peroxide which is decomposable at a low temperature (50 to 130 °C ) and a polyfunctional compound (as cross linking agents), the composition is applicable in situ for providing gaskets and can be vulcanized by being subjected to a hot-air atmosphere of 60 to 150 °C .
- Gaskets for motor vehicles were prepared from compositions comprising components listed in Table 1 below.
- Gaskets for motor vehicles were prepared in the same manner as in Example 1 from a composition obtained by blending the compositions of Comparative Examples 2 and 3 in the ratio of 50 : 50 by weight.
- table 1 G702 : vinylidene fluoride/hexafluoropropylene copolymer, product of Daikin Industries, Ltd.
- FAU-014Y copolymer of G702/nBuAc/1,6-HXA(70/27/3)
- nBuAc n-Butyl acrylate
- 1,6-HXA 1,6-Hexanediol diacrylate
- Naugard 445 Age resistor, product of Uniroyal Chemical Co., Ltd.
- the gasket of the invention for motor vehicle engines and transmissions has outstanding heat resistance, mechanical strength when hot and resistance to engine oil bubbling. Further, the gasket of the invention for motor vehicle engines and transmissions is excellent in compression set, ATF resistance, LLC resistance and durability.
Abstract
A gasket for automotive engine transmission, made from a cross-linking composition comprising 100 parts by weight of a polymer prepared by dissolving or swelling a noncrystalline fluoropolymer in an acrylic monomer and polymerizing the monomer, 0.1 to 100 parts by weight of a filler, and 0.1 to 10 parts by weight of a cross-linking agent. This gasket is excellent in mechanical strength and resistance to engine oil bubbling at high temperatures and also in compression set, resistances to automatic transmission fluid and long-life coolant, and durability.
Description
- The present invention relates to gaskets for motor vehicle engines and transmissions.
- Gaskets for motor vehicles are used for sealing off the covers to be attached to the cylinder heads of motor vehicle internal combustion engines, and can be checked for suitability including that of the material thereof when subjected to thermal loads and vibrations during operation. More specifically, they must be resistant to cold for starting engines in a cold state and resistant to heat under high-speed loads. If the engine oil or transmission oil leaks owing to a temperature difference between the intake side and the exhaust side of the engine or to the angle at which the engine is mounted on the vehicle, the oil will drip onto the exhaust pipe in view of the construction of the engine, so that the gasketed portion is exposed to a great fire hazard.
- While such gaskets for motor vehicle engines and transmissions have heretofore been prepared from an acrylic elastomer or fluorine-containing polymer, the former has the drawback of being inferior in heat resistance, mechanical strength when hot and resistance to engine oil bubbling. Although the latter is satisfactory in heat resistance and resistance to engine oil bubbling, the material has the drawback of being very low in mechanical strength when hot.
- Accordingly, we prepared gaskets for motor vehicle engines and transmissions from a blend of both acrylic elastomer and fluorine-containing polymer. Unexpectedly, however, we found that the gaskets were seriously inferior in all the properties of heat resistance, mechanical strength when hot and resistance to engine oil bubbling. This is apparent from the comparative example given later.
- An object of the present invention is to provide a gasket for motor vehicle engines and transmissions which is made of a vulcanized rubber prepared from a homogeneous dispersion of fluorine-containing polymer and acrylic elastomer and not undergoing phase separation, the gasket having outstanding heat resistance, mechanical strength when hot and resistance to engine oil bubbling as characteristics imparted thereto by the respective materials.
- Another object of the invention is to provide a gasket for motor vehicle engines and transmissions which is excellent also in compression set (CS), resistance to ATF (Automatic Transmission Fuel), resistance to LLC (Long Life Coolant) and durability.
- The present invention provides a gasket for motor vehicle engines and transmissions which is prepared from a crosslinkable composition comprising 100 parts by weight of a polymer, 0.1 to 100 parts by weight of a filler and 0.1 to 10 parts by weight of a crosslinking agent, the polymer being obtained by dissolving or swelling an amorphous fluorine-containing polymer in an acrylic monomer and subsequently polymerizing the monomer into a high polymer.
- We have conducted intensive research in order to prepare homogeneous dispersions from fluorine-containing polymers and acrylic elastomers and to cause the two comonents to retain compatibility with each other after a heat treatment for vulcanization, and consequently prepared a gasket for use in motor vehicle engines and transmissions from a crosslinkable composition which is obtained by dissolving or swelling a fluorine-containing polymer in an acrylic monomer, thereafter polymerizing the acrylic monomer to prepare a polymer and admixing a filler and a crosslinking agent with the polymer. We have found that the gasket has outstanding properties in respect of heat resistance, mechanical strength in a hot state and resistance to engine oil bubbling which properties are unexpectable from mere blends of fluorine-containing polymers and acrylic elastomers as kneaded together.
- The gasket of the invention for motor vehicle engines and transmissions is excellent also in compression set, ATF resistance, LLC resistance and durability.
- Examples of amorphous fluorine-containing polymers which can be dissolved or swollen in acrylic monomers for use in the present invention are vinylidene fluoride/hexafluoropropylene, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene, vinylidene fluoride/chlorotrifluoroethylene and like vinylidene fluoride copolymers, tetrafluoroethylene/propylene, hexafluoropropylene/ethylene and fluoro(alkyl vinyl ether) (including those having a multiplicity of ether bonds)/olefin copolymers, fluorosilicone rubber, fluorophosphazene rubber, etc. Preferable among these are vinylidene fluoride/hexafluoropropylene, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene and vinylidene fluoride/chlorotrifluoroethylene polymers.
- The term "amorphous" as used herein refers to elastomers the melting point of which is not observable substantially at the peak of DSC (Differential Scanning Colorimeter).
- Acrylic monomers for use in the present invention are not limited and include mono- and poly- functional monomers. Such monomers are used singly, or at least two of them are used in combination. Preferably, polyfunctional monomers are used in a small amount in combination with a monofunctional monomer. Examples of preferred monomers are methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), 2-hydroxyethyl methacrylate (HEMA), glycidyl methacrylate (GMA), 2-methoxyethyl methacrylate (MEMA), 3-(trimethoxysilyl)propyl methacrylate (MSPM), 2-(phenylphosphoryl)ethyl methacrylate (phenyl-P), 2-hydroxy-3-(β-napthoxy)propyl methacrylate (HNPM), N-phenyl-N-(2-hydroxy-3-methacryloxy)propylglycine (NPG-GMA), ethylene glycol dimethacrylate (EDMA or 1G), diethylene glycol dimethacrylate (DiEDMA or 2G), triethylene glycol dimethacrylate (TriEDMA or 3G), tetraethylene glycol dimethacrylate (TEDMA or 4G), 1,4-butanediol dimethacrylate (1,4-BuDMA), 1,3-butanediol dimethacrylate(1,3-BuDMA), 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (Bis-GMA), 2,2-bis(4-methacryloxyphenyl)propane (BPDMA), 2,2-bis(4-methacryloxyethoxyphenyl)propane (Bis-MEPP), 2,2-bis(4-methacryloxypolyethoxyphenyl)propane (Bis-MPEPP), di(methacryloxyethyl)trimethylhexamethylenediurethane (UDMA), trimethylolpropanetrimethacrylate (TMPT),
CH₂ = C(CH₃)COOCH₂CF₃ (3FMA),
CH₂ = C(CH₃)COOCH₂CF₂CF₂H (4FMA),
CH₂ = C(CH₃)COOCH₂CF₂CF₃ (5FMA),
CH₂ = C(CH₃)COOCH₂(CF₂)₂CF₃ (7FMA),
CH₂ = C(CH₃)COOCH₂(CF₂)₃CF₂H (8FMA),
acrylates and α - fluoroacrylates corresponding to such compounds. - Examples of α -fluoroacrylates are
CH₂ = CFCOOCH₂CF₂CF₂H (4FFA),
CH₂ = CFCOOCH₂CF₂CF₃ (5FFA),
CH₂ = CFCOOCH₂(CF₂)₃CF₂H (8FFA) and
CH₂ = CFCOOCH₂(CF₂)₅CF₂H (12FFA). - To modify the monomer, the monomer may have admixed therewith a small amount of acrylonitrile, 2-chloroethyl vinyl ether, vinyl monochloroacetate, methylvinyldichlorosilane or the like. When the polyfunctional monomer is to be used, it is suitable to use the polyfunctional monomer in an amount of 1 to 20 parts (by weight, the same as hereinafter) per 100 parts by weight of the monofunctional monomer.
- The proportions of the amorphous fluorine-containing polymer and the acrylic monomer to be used in the present invention can be determined suitably. It is generally desirable to use 5 to 1000 parts of the latter per 100 parts of the former.
- According to the present invention, the fluorine-containing polymer is dissolved or swollen in the acrylic monomer, which is then polymerized into a high polymer. The polymerization is conducted in the presence of a polymerization initiator. A polymerization inhibitor, reducing agent, transfer agent, etc. can be added to the polymerization system. Examples of useful polymerization initiators are light, heat, benzoyl peroxide, azoisobutyronitrile (AIBN), camphorquinone (CQ), 9-fluorenone, tributylborane (TBB), benzophenone and the like. Examples of useful reducing agents are dimethylaminoethyl methacrylate (DMAEMA), dimethyl-p-toluidine (DMPT) and the like. Examples of useful polymerization inhibitors are hydroquinone, hydroquinone methyl ester and the like. Examples of useful transfer agents include lauryl mercaptan.
- Cross linking of the composition of the invention or use of the polyfunctional acrylic monomer forms an IPN (interpenetrating polymer network). IPN is a polymer obtained by mixing two linear polymers together each in the form of a liquid (or solution) and crosslinking one or both of the polymers to interlock the respective molecular chains. When IPN is to be formed according to the invention, the following method is usually employed. A monomer for forming a guest polymer is injected into the high polymer formed. Alternatively, the polymer is immersed in or injected into a solution containing the monomer. The mixture is then polymerized by heating, irradiation with light or like procedure, a filler, crosslinking agent, etc. are admixed with the resulting polymer, and the mixture is crosslinked. Other methods are also usable.
- Examples of fillers useful for the present invention are carbon black, silica, clay, kieselguhr, talc, calcium carbonate and like reinforcing agents. The filler is used preferably in an amount of 0.1 to 100 parts per 100 parts of the polymer. If the amount is less than 0.1 part, an insufficient reinforcing effect will result, whereas if the amount is over 100 parts, the composition fails to exhibit rubberlike properties.
- Examples of crosslinking agents useful for the invention are those for use in crosslinking vinylidene fluoride-containing rubbers, such as peroxides, polyols and polyamines. More specific examples are Perhexa 2.5B (peroxide manufactured by Nippon Oils & Fats Co., Ltd.), triallyl isocyanurate (TAIC) bisphenol AF, N,N'-dicinnamylidene-1,6-hexadiamine, etc. The crosslinking agent is used preferably in an amount of 0.1 to 10 parts per 100 parts of the polymer. If the amount is less than 0.1 part, the degree of crosslinking achieved is insufficient, whereas if the amount is in excess of 10 parts, the composition is unlikely to exhibit rubberlike properties.
- When required, also usable are nitrogen- or phosphorus- containing organic tertiary or quaternary compounds as crosslinking accelerators, oxides or hydroxides of bivalent metals as an acid-acceptor, and compounds containing a plurality of vinyl or allyl groups and serving as auxiliary crosslinking agents. Further usable as required are antioxidants, processing assisting agents, scorch retarders, antiozonants, ultraviolet absorbers, flame retardants, plasticizers and other additives.
- The gasket for motor vehicle engines and transmissions which is obtained according to the invention by dissolving or swelling the fluorine-containing polymer in the acrylic monomer and subsequently polymerizing the monomer is unexpectedly exceedingly superior in heat resistance, mechanical strength when hot and resistance to engine oil bubbling to those obtained from a mere blend of fluorine-containing polymer and acrylic elastomer.
- The gasket of the invention for motor vehicle engines and transmissions is excellent also in compression set, ATF resistance, LLC resistance and durability.
- The composition of the invention has a slightly higher viscosity than usual simple blended rubber materials, so that when comprising a peroxide which is decomposable at a low temperature (50 to 130 °C ) and a polyfunctional compound (as cross linking agents), the composition is applicable in situ for providing gaskets and can be vulcanized by being subjected to a hot-air atmosphere of 60 to 150 °C .
- Examples and Comparative Examples are given below. In these examples, the parts and percentages are all by weight.
- Gaskets for motor vehicles were prepared from compositions comprising components listed in Table 1 below.
- Gaskets for motor vehicles were prepared in the same manner as in Example 1 from a composition obtained by blending the compositions of Comparative Examples 2 and 3 in the ratio of 50 : 50 by weight.
In table 1 :
G702 : vinylidene fluoride/hexafluoropropylene copolymer, product of Daikin Industries, Ltd.
FAU-014Y: copolymer of G702/nBuAc/1,6-HXA(70/27/3)
nBuAc : n-Butyl acrylate
1,6-HXA : 1,6-Hexanediol diacrylate
Naugard 445 : Age resistor, product of Uniroyal Chemical Co., Ltd.Table 1 Example 1 Comparative Example 1 2 3 4 Halogen-containing acrylic rubber - 100 100 - 30 G 702 - - - 100 70 FAU-014Y 100 - - - - Stearic acid - 1 1 - 1 MgO - - - 6.0 4.2 HAF Carbon - 65 60 - 65 MT Carbon 20 - - 20 - Plasticizer - - 5 - - Sulfur - 0.3 - - - Potassium stearate - 0.5 - - - Sodium stearate - 3.0 - - - Zinc-di-n-butylthiocarbamate - - 1.5 - 0.5 2,4,6-Trimercapto-S-triazine - - 0.5 - 0.2 Ca(OH)₂ - - - 3.0 2.1 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane 1.5 - - - - Triallyl isocyanurate 4 - - - - Naugard 445 0.6 - - - - - The properties of the foregoing compositions were evaluated by the following methods. Table 2 shows the results.
- (1) Tensile strength (T b) : According to JIS 6301.
- (2) Tear strength (T R) : According to JIS 6301.
- (3) Compression set (CS) : According to JIS 6301.
- (4) German low temperature-torsional test : Measured according to JIS 6301 using refrigerant isopropyl alcohol (IPA).
- (5) Resistance to engine oil bubbling : Measured using Nissan Extra Save X (7.5W-30), 150°C × 72hr
- (6) ATF resistance : 150°C × 72hr, Castle fluid Dexron 2
- (7) LLC resistance 120°C × 48hr, Toyota genuine LLC and water (1:1 vol ratio)
- (8) Heat resistance : 175°C × 500hr
- (9) Durability : The gasket tested was 5 × 9mm in cross section and having a cover groove measuring 5 × 6mm.
- (a) Initial assembling bearing pressure : At least 30kgf/cm², 30 % compression.
- (b) Initial sealing property : At least 2 kgf/cm² in bearing pressure, 30 % compression.
- (c) Crack resistance : 6 mm in groove depth, 9 mm in height, 3 mm in exposed part, 50 % compression, 150°C × 24hr, 5 cycles.
- (d) Continuous high-speed endurance : 30 % compression, 150°C × 500hr
- (e) Thermal shock leak endurance : 30 % compression, (150°C × 15hr) + (-30°C × 9hr), 20 cycles, filled with oil and free of pressure, was subjected to thermal shock, and checked for leakage with reference to a color change in micro-check indicating oozing oil.
- The gasket of the invention for motor vehicle engines and transmissions has outstanding heat resistance, mechanical strength when hot and resistance to engine oil bubbling. Further, the gasket of the invention for motor vehicle engines and transmissions is excellent in compression set, ATF resistance, LLC resistance and durability.
Claims (8)
- A gasket for motor vehicle engines and transmissions which is prepared from a crosslinkable composition comprising 100 parts by weight of a polymer, 0.1 to 100 parts by weight of a filler and 0.1 to 10 parts by weight of a crosslinking agent, the polymer being obtained by dissolving or swelling an amorphous fluorine-containing polymer in an acrylic monomer and subsequently polymerizing the monomer into a high polymer.
- A gasket for motor vehicle engines and transmissions as defined in claim 1 wherein the amorphous fluorine-containing polymer is vinylidene fluoride/hexafluoropropylene, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene, vinylidene fluoride/chlorotrifluoroethylene and like vinylidene fluoride copolymer, tetrafluoroethylene/propylene, hexafluoropropylene/ethylene and fluoro(alkyl vinyl ether)(including those having a multiplicity of ether bonds)/olefin copolymer, fluorosilicone rubber or fluorophosphazene rubber.
- A gasket for motor vehicle engines and transmissions as defined in claim 2 wherein the amorphous fluorine-containing polymer is vinylidene fluoride/hexafluoropropylene, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene or vinylidene fluoride/chlorotrifluoroethylene copolymer.
- A gasket for motor vehicle engines and transmissions as defined in claim 1 wherein, as the acrylic monomer, the monofunctional acrylic monomer and the polyfunctional acrylic monomer are used conjointly.
- A gasket for motor vehicle engines and transmissions as defined in claim 1 wherein the polyfunctional monomer is used in an amount of 1 to 20 parts by weight per 100 parts by weight of the monofunctional monomer.
- A gasket for motor vehicle engines and transmissions as defined in claim 1 wherein the acrylic monomer is used in an amount of 5 to 1000 parts by weight per 100 parts of the amorphous fluorine-containing polymer.
- A gasket for motor vehicle engines and transmissions as defined in claim 1 wherein the filler is carbon black, silica, clay, kieselguhr, talc or calcium carbonate.
- A gasket for motor vehicle engines and transmissions as defined in claim 1 wherein the crosslinking agent is peroxide, polyol or polyamine.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4139872A JPH06172743A (en) | 1992-04-30 | 1992-04-30 | Gasket for automotive engine and transmission |
JP139872/92 | 1992-04-30 | ||
PCT/JP1993/000571 WO1993022586A1 (en) | 1992-04-30 | 1993-04-28 | Gasket for automotive engine transmission |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0592691A1 true EP0592691A1 (en) | 1994-04-20 |
EP0592691A4 EP0592691A4 (en) | 1994-09-28 |
Family
ID=26434390
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP9393911954A Withdrawn EP0592691A4 (en) | 1992-04-30 | 1993-04-28 | Gasket for automotive engine transmission |
Country Status (1)
Country | Link |
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EP (1) | EP0592691A4 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0857757A1 (en) * | 1997-02-11 | 1998-08-12 | Ausimont S.p.A. | Blends of fluorinated and acrylic elastomers |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0385443A2 (en) * | 1989-02-28 | 1990-09-05 | Daikin Industries, Limited | Polymer material having shape memory characteristics |
EP0481372A2 (en) * | 1990-10-13 | 1992-04-22 | Daikin Industries, Limited | Crosslinkable composition |
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1993
- 1993-04-28 EP EP9393911954A patent/EP0592691A4/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0385443A2 (en) * | 1989-02-28 | 1990-09-05 | Daikin Industries, Limited | Polymer material having shape memory characteristics |
EP0481372A2 (en) * | 1990-10-13 | 1992-04-22 | Daikin Industries, Limited | Crosslinkable composition |
Non-Patent Citations (1)
Title |
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See also references of WO9322586A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0857757A1 (en) * | 1997-02-11 | 1998-08-12 | Ausimont S.p.A. | Blends of fluorinated and acrylic elastomers |
US5902860A (en) * | 1997-02-11 | 1999-05-11 | Ausimont S.P.A. | Blends of fluorinated and acrylic elastomers |
Also Published As
Publication number | Publication date |
---|---|
EP0592691A4 (en) | 1994-09-28 |
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